CN1168775C - Melt tension improver for polyolefen resins and process for producing the same - Google Patents
Melt tension improver for polyolefen resins and process for producing the same Download PDFInfo
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- CN1168775C CN1168775C CNB98809360XA CN98809360A CN1168775C CN 1168775 C CN1168775 C CN 1168775C CN B98809360X A CNB98809360X A CN B98809360XA CN 98809360 A CN98809360 A CN 98809360A CN 1168775 C CN1168775 C CN 1168775C
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
A melt tension enhancer for polyolefin resins that contains polytetrafluoroethylene and a polymer of an alkyl (meth)acrylate of 5-30 carbon atoms, and a process for its production. Its addition to polyolefin resins enhances the melt tension of the polyolefin resins without impairing the surface appearance of their molds.
Description
Technical field
The present invention relates to melt tension toughener that polyolefin resin uses with and preparation method thereof, this melt tension toughener contains (A) tetrafluoroethylene and (B) based on the polymkeric substance of (methyl) alkyl acrylates of 5～30 carbon atoms.
Background technology
Polyolefin resin is low-cost and good physicals owing to it, is widely used in the past in many moulded products.Yet, (below be called " melt tension ") is lower because tension force during its fusion, for example for polypropylene, so there are some defective in they on processing characteristics, comprise relatively poor vacuum formability, blow molding, foaming, extrusion moulding and calendering formation.
Polyethylene etc. are often with polypropene blended, and improving these processing characteristicies, but because therefore the improvement deficiency of processing characteristics needs a large amount of polyethylene, and that the shortcoming that this brings is the hardness of gained blend is lower.Someone attempts improving melt tension by improving polyolefinic molecular weight, but the molecular weight height also can bring problem, because it has reduced the flowing property of melt, melt flowability is a parameter of processing characteristics, therefore can not obtain suitable balance between melt tension and melt flowability.
As having the polyolefin resin that improves processing characteristics, in Japanese Unexamined Patent Publication 62-121704, Japanese Unexamined Patent Publication 2-298536 and some other, the polypropylene with free end capped (free-ended) long chain branched is disclosed.This polyacrylic unique visco-elasticity makes and can keeps the resin film strength in foamed forming process, therefore can make conventional straight chain polypropylene can not obtain, have a highly foam of separate chamber.Yet, because such polypropylene needs particular processing method or synthetic method, comprise electron beam irradiation or add superoxide that forming free end capped long chain branched, so its shortcoming is that the production cost of resin greatly increases.
On the other hand, metallocene is compared with common catalyzer with the methylaluminoxane as promotor, has the height homogeneity on the activity, they have good copolymerization performance, and can make the polyethylene of molecular weight distribution and composition narrowly distributing under high reactivity.The polyolefine that is made by metallocene catalyst has good heat sealability and thermal viscosity, but their narrow molecular weight distributions causes its melt tension low, and therefore existing problems are known on moulding processability; Therefore still be desirably on the melt tension and improve to some extent.
The degree of crystallinity height and the intermolecular forces of tetrafluoroethylene are less, therefore it can become fibrous under slight stress, it combines with thermoplastic resin improved moulding processability and mechanical property can be provided simultaneously, so it little by little is used as the additive of thermoplastic resin.
For example, Japanese Unexamined Patent Publication 5-214184 and 6-306212 disclose and have contained the resin combination that adds polyolefinic tetrafluoroethylene.Have again, Japanese Unexamined Patent Publication 7-324147 discloses a kind of method for preparing polyolefine resin composition, this resin combination obtains by mix tetrafluoroethylene and a kind of dispersion medium powder under high-shear, wherein is mixed into polyolefine after fibrous in that tetrafluoroethylene is.In addition, Japanese Unexamined Patent Publication 9-25420 discloses a kind of like this method, and this method is used the tetrafluoroethylene of sealing with styrene-acrylonitrile copolymer, to improve the melting rate of various resins such as polyvinyl chloride (PVC) RESINS.
Yet, the shortcoming of tetrafluoroethylene is the bad dispersibility in the thermoplastic resin of common not halogen atom, and as described in Japanese Unexamined Patent Publication 5-214184 and 6-306212, it can not form uniform dispersion by simple blend, has therefore reduced the appearance of moulded products significantly.
Even with the method for Japanese Unexamined Patent Publication 7-324147, it is fibrous also to be difficult to by shearing force all tetrafluoroethylene to be presented, and therefore fibrous tetrafluoroethylene also can be assembled in matrix resin, makes to obtain uniform composition.
And, although the method for Japanese Unexamined Patent Publication 9-25420 is attempted the affinity of improving itself and matrix resin by sealing, improving aspect its dispersed in polyolefin resin still to no effect.
In other words, all these methods still can not solve the dispersion problem of tetrafluoroethylene in polyolefin resin, and the defective of bringing is to need a large amount of tetrafluoroethylene so that it has above-mentioned useful performance, and the appearance of moulded products is impaired.
Disclosure of the Invention
An object of the present invention is to provide a kind of melt tension toughener, this toughener can improve the dispersiveness of tetrafluoroethylene in polyolefin resin, and can improve polyolefinic moulding processability, and does not damage the appearance of moulded products.
For overcoming the problems referred to above, the inventor has done intensive research, the result has finished the present invention based on following discovery, promptly by in polyolefin resin, adding the resin combination of the polymkeric substance contain tetrafluoroethylene and a kind of (methyl) alkyl acrylate based on 5～30 carbon atoms, can improve the melt tension of polyolefin resin, and not damage the appearance of moulded products.
Therefore the invention provides melt tension toughener that a kind of polyolefin resin uses and preparation method thereof, this melt tension toughener contains (A) tetrafluoroethylene and (B) based on the polymkeric substance of (methyl) alkyl acrylates of 5～30 carbon atoms.
Implement best mode of the present invention
Example as the used polyolefin resin of the present invention, can mention such resin, its main component is the homopolymer of the olefinic monomer that obtained by radical polymerization, ionic polymerization etc. or the multipolymer of olefinic monomer, the olefinic monomer of the amount of occupying the majority and the monomeric multipolymer of small amount of ethylene base, or the multipolymer of olefinic monomer and diolefinic monomer, and above-mentioned these can use separately or with two or more blended forms.The used polymerizing catalyst of these resins is known, as Ziegler catalyst, chrome catalysts or metallocene catalyst.
As olefinic monomer described here, that can mention has ethene, propylene, and 1-butylene, the 1-hexene, 1-decene, the 1-octene, 4-methyl-1-pentenes etc. particularly preferably are ethene and propylene in the middle of them.As the homopolymer of these olefinic monomers or the specific examples of multipolymer, that can mention has a new LDPE (film grade), very low density polyethylene, ultra-low density polyethylene, LLDPE, high density polyethylene(HDPE), ultrahigh molecular weight polyethylene(UHMWPE), polypropylene, ethylene-propylene copolymer, polymethylpentene, polybutene etc.These olefin polymers can use separately or with two or more blended forms.Particularly preferably be main component in the middle of these and be selected from the polyolefin resin of the mixture of polyethylene, polypropylene and ethylene-propylene copolymer for one or more.
(A) tetrafluoroethylene in the melt tension toughener of the present invention can be obtained by the monomer component polymerization that mainly is made of tetrafluoroethylene by known method.Component as copolymerization, (A) tetrafluoroethylene can contain Fluorine containing olefine, as R 1216, a chlorotrifluoroethylene, fluoro-alkyl ethene, perfluoroalkyl vinyl ether etc., and fluorine-containing (methyl) alkyl acrylate, as (methyl) perfluoroalkyl acrylate, as long as original performance of tetrafluoroethylene is not lowered.Based on the amount of tetrafluoroethylene, preferred copolymerization components contents is not more than 10 weight %.
In the melt tension toughener of the present invention can be based on (B) polymkeric substance of (methyl) alkyl acrylates of 5～30 carbon atoms by radical polymerization, ionic polymerization etc., the polymerization of the monomer component of (methyl) alkyl acrylate by containing 5～30 carbon atoms obtains.Specific examples as (methyl) alkyl acrylates of 5～30 carbon atoms, that can mention has (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid stearyl and (methyl) isobornyl acrylate.These monomers can use separately or with two or more blended forms.
As the monomer that can close with (methyl) alkyl acrylate copolymer of 5～30 carbon atoms, the monomer that styrene-based is arranged that can mention, as vinylbenzene, p-methylstyrene, o-methyl styrene, to chloro-styrene, chloro styrene, to methoxy styrene, O-methoxy vinylbenzene, 2,4-dimethyl styrene and alpha-methyl styrene; (methyl) alkyl acrylate monomer of 1～4 carbon atom is as (methyl) methyl acrylate, (methyl) ethyl propenoate and (methyl) butyl acrylate; Vinyl cyanide monomer is as vinyl cyanide and methacrylonitrile; Vinyl ether monomers is as vinyl methyl ether and EVE; The vinyl carboxylates monomer is as vinyl acetate and vinyl butyrate; Olefinic monomer is as ethene, propylene and iso-butylene; And diene monomers, as divinyl, isoprene, dimethylbutadiene etc.These monomers can use separately or with two or more blended forms.
Melt tension toughener of the present invention contains (A) tetrafluoroethylene and (B) based on the polymkeric substance of (methyl) alkyl acrylates of 5～30 carbon atoms, wherein the weight ratio of (B)/(A) is preferably 0.2～100, and more preferably 0.5～50.If weight ratio (B)/(A) is less than 0.2, then the dispersiveness of tetrafluoroethylene can be lowered.When greater than 100 the time, can not obtain the effect of tetrafluoroethylene.
Based on the gross weight of melt tension toughener, the amount of tetrafluoroethylene in melt toughener of the present invention is preferably 0.05～40 weight %.When less than 0.05 weight %, will have to add too in a large number obtaining enough melt tensions, and the hardness of polyolefin resin and thermotolerance will suffer damage.When greater than 40 weight %, the dispersiveness of tetrafluoroethylene can reduce.
By mixing this melt tension toughener, feasible polyolefin resin for 100 weight parts, the content of tetrafluoroethylene is 0.001～20 weight part, can obtain having the polyolefine resin composition of gratifying processability, the polytetrafluoroethyl-ne olefinic constituent is evenly dispersed in the polyolefin resin with tiny fiber condition, this resin combination has improved melt tension, and does not damage the appearance of moulded products.
Melt tension toughener of the present invention can be obtained by first method as described below by powder type, water dispersion and the particle diameter that with particle diameter is the polytetrafluoroethylparticle particle of 0.05～1.0 μ m in the method be 0.05～1.0 μ m, mix based on the water dispersion of the polymer particle of (methyl) alkyl acrylates of 5～30 carbon atoms, and with this mixture coagulated or spraying drying.Also can obtain its powder by second method as described below, be in the dispersion 0.05～1.0 μ m, containing polytetrafluoroethylparticle particle that particle diameter is 0.05～1.0 μ m and particle diameter in this method based on the mixture of the water dispersion of the polymer particle of (methyl) alkyl acrylates of 5～30 carbon atoms, make a kind of monomer polymerization that ethene belongs to unsaturated link(age) that contains, then with product cohesion or spraying drying.
The water dispersion that is used to prepare the polytetrafluoroethylparticle particle of melt tension toughener of the present invention can obtain by the letex polymerization of the monomer component that mainly is made of tetrafluoroethylene.
Representative goodss raw material as the polytetrafluoroethylparticle particle dispersion, that can mention has Fluon AD-1 and an AD-936 (trade mark) that is produced by Asahi ICI Fluoropolymers, the Polyflon D-1 and the D-2 (trade mark) that produce by Daikin Industries, and the Teflon 30J (trade mark) that produces by Mitsui-DuPont Fluorochemicals.
What be used to prepare melt tension toughener of the present invention can be by known emulsion polymerisation process or microemulsion polymerization method based on the water dispersion of the polymer particle of (methyl) alkyl acrylates of 5～30 carbon atoms, and the polymerization of the monomer component of (methyl) alkyl acrylate by containing 5～30 carbon atoms obtains.
In second kind of preparation method of melt tension toughener of the present invention, to being that the water dispersion and the particle diameter of the polytetrafluoroethylparticle particle of 0.05～1.0 μ m is 0.05～1.0 μ m's containing particle diameter, based in the dispersion of the mixture of the water dispersion of the polymer particle of (methyl) alkyl acrylates of 5～30 carbon atoms further polymeric contain the monomer that ethene belongs to unsaturated link(age) and have no particular limits, it can be selected from the monomer of styrene-based, as vinylbenzene, p-methylstyrene, o-methyl styrene, to chloro-styrene, chloro styrene, to methoxy styrene, O-methoxy vinylbenzene, 2,4-dimethyl styrene and alpha-methyl styrene; (methyl) acrylate monomer is as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) cyclohexyl acrylate, (methyl) glycidyl acrylate and (methyl) vinylformic acid 2-hydroxyl ethyl ester; Vinyl cyanide monomer is as vinyl cyanide and methacrylonitrile; Vinyl ether monomers is as vinyl methyl ether and EVE; The vinyl carboxylates monomer is as vinyl acetate and vinyl butyrate; Olefinic monomer is as ethene, propylene and iso-butylene; And diene monomers, as divinyl, isoprene, pentadiene (prene), dimethylbutadiene etc.These monomers also can use separately or with two or more blended forms.
Can mediate or the roll-type kneading as extruding by known method, melt tension toughener of the present invention be joined in the polyolefin resin by melt kneading.Perhaps available multistep processes is mixed, and wherein melt tension toughener of the present invention is mixed with a part of polyolefin resin, prepares a kind of masterbatch, joins in the masterbatch remaining polyolefin resin and mixing after this.
The polyolefine resin composition that contains melt tension toughener of the present invention has the melt tension of raising, tensile property when it has improved calendering, the drawdown of molten resin when thermoforming or blow molding (draw down), and the perforate during foaming forms, and improved the general processing characteristics of calendering, thermoforming, blow molding and foaming etc.Discharging volume when it has improved extrusion moulding simultaneously and the surface appearance of extrusion moulding product such as sheet material and film, and extrude processing characteristics.The bulk of the not having tetrafluoroethylene simultaneously phenomenon of condensing, so the appearance of moulded products is good.
Also can in the polyolefine resin composition that is added with melt tension toughener of the present invention, add filler.Based on 100 weight part polyolefine resin compositions, the content of filler is preferably 0.1～400 weight part, adds filler and can improve hardness and thermotolerance, improves processing characteristics such as drawability, is adhered on the surface of roller preventing, and realizes the reduction of cost.When filler content during less than 0.1 weight part, the effect deficiency that hardness is improved, when greater than 400 weight parts, surface quality can reduce.As representational filler, that can mention has lime carbonate, talcum, glass fibre, magnesiumcarbonate, mica, kaolin, calcium sulfate, barium sulfate, titanium white, white carbon black, carbon black, ammonium hydroxide, magnesium hydroxide, an aluminium hydroxide etc.Preferably lime carbonate and talcum in the middle of these.
If need, the polyolefine resin composition that has added the melt tension toughener also can further contain other additive, as stablizer, lubricant, fire retardant etc.Their each representative example that can mention comprise, stablizer has phenol stabilizer, [3-(3 as tetramethylolmethane four, 5-di-t-butyl-4-hydroxyphenyl) propionic ester], triglycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionic ester] is based on the stablizer of phosphorus, as three (single nonyl phenyl) phosphorous acid ester and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, and based on the stablizer of sulphur, as the dilauryl thiodipropionate; Lubricant has lauric acid, palmitinic acid, oleic acid or stearic sodium salt, calcium salt or magnesium salts; Fire retardant has phosphate compound, comprises trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenylphosphate, Tritolyl Phosphate, tolyl phenyl phosphate ester, the octyl group diphenyl phosphoester, diisopropyl phenyl phosphoric acid ester, tricresyl phosphate (chloroethyl) ester, polyphosphate is as the dihydroxyphenyl propane bisphosphate that alkoxyl group replaces, quinhydrones bisphosphate, resorcinol diphosphate, three oxygen base benzene triguaiacyl phosphates; Tetrabromo-bisphenol, decabromo-diphenyl oxide, hexabromocyclododecane, eight bromo diphenyl ethers, two tribromophenoxy ethane, ethylenebis tetrabromo phthalimide, tribromophenol, halogenated compound comprises the various halogenated epoxy oligopolymers that obtained by halogenated dihydroxyphenyl propane and epichlorohydrin reaction, has the carbonic ether oligopolymer of halogenated bisphenol A as structural constituent, halogenated polystyrene, chlorinatedpolyolefins, polyvinyl chloride, and metal hydroxides, metal oxide, sulphonamide oxide compound etc.
The working method that adds the polyolefine resin composition that melt tension toughener of the present invention is arranged can be the method such as calendering, thermoforming, blow molding, foaming, extrusion moulding, injection molding or melt spinning.
Adding has the polyolefine resin composition of melt tension toughener of the present invention to can be used for making useful moulded products, comprises sheet material, film, thermoforming thing, hollow mould goods, foam, extrusion moulding product, fiber etc.
Therefore, the present invention also provides a kind of method for preparing polyolefin resin foam, this method is included in melt kneading polyolefin resin of the present invention melt tension toughener, polyolefin resin and whipping agent in the forcing machine, extrudes this mixture by a mouth mould that is installed in the forcing machine end under lower blow(ing) pressure then.
Simultaneously, the present invention also provides a kind of method for preparing polyolefin resin foam, this method is included in the polyolefine resin composition and the whipping agent of melt kneading the invention described above in the forcing machine, extrudes this mixture by the mouth mould that is installed in the forcing machine end under lower blow(ing) pressure then.
In the above-mentioned method for preparing polyolefin resin foam, polyolefin resin can be essentially no crosslinked acrylic resin.
In addition, the present invention also provides a kind of circulation means of polyolefin resin goods, wherein for recycling, polyolefin resin goods waste material is cut or pulverizes and carries out the heat fusing moulding, this method comprises adding polyolefin resin of the present invention melt tension toughener in polyolefin resin goods waste material, wherein based on the polyolefin resin in the described polyolefin resin goods of the 100 weight parts waste material, (A) content of tetrafluoroethylene is 0.001～20 weight part.
Further describe the present invention by embodiment now, but should be understood that, the present invention is subjected to the restriction of these embodiment never in any form.
In the following description, " part " and " % " all by weight.
According to following mensuration of carrying out the different performance that in reference example, embodiment and Comparative Examples, provides.
(1) solids concn: 170 ℃ of following drying particulate dispersions 30 minutes.
(2) size distribution and weight average particle diameter: the dilute with water particle dispersion is as sample solution, and by dynamic light scattering determination (by Otsuka Denshi, the ELS800 (trade mark) that KK. produces, temperature: 25 ℃, scattering angle: 90 °).
(3) ξ electromotive force: with the NaCl aqueous solution diluent particles dispersion of 0.01mol/L as sample solution, and by electrophoresis technique determining (by Otsuka Denshi, the ELS800 that KK. produces, temperature: 25 ℃, scattering angle: 10 °).
(4) melt tension: with stream (falling flow) tester (Capillograph (trade mark) that Toyo Seiki produces) that falls with constant rate of extrusion (10mm falling velocity/minute) extruded polyolefin resin combination pellet, extrude the line material with constant speed (4m/min) pulling, and measure melt tension.The L/D of mouth mould is 10.0mm/ φ 2.0mm, and measuring temperature is 200 ℃.
(5) ratio of expansion: with the current test instrument that falls (Capillograph that Toyo Seiki produces) with constant rate of extrusion (1.5mm falling velocity/minute) extrusion resin composition pellet, the 5mm place measures the diameter (D) of line material under nozzle, and calculates with following equation.The L/D of mouth mould is 10.0mm/ φ 2.0mm, and measuring temperature when also containing polypropylene is 190 ℃, and measuring temperature when only polyethylene being arranged is 160 ℃.
(ratio of expansion)=D (mm)/2.0
(6) melt flow rate (MFR):, the resin combination pellet is measured with the load of 2.16kg according to the method for ASTM D1238.Measuring temperature when also containing polypropylene is 230 ℃, and measuring temperature when only polyethylene being arranged is 190 ℃.
(7) Young's modulus: with the injection molding of resin combination pellet is testing plate, according to the method for ASTM D790 it is measured.
(8) outward appearance of roll-in sheet material: use the resin combination pellet, the outward appearance of pair roller laminated sheet is carried out the naked eyes evaluation in the roll mixing process.
Zero: no irregular place, surface, gloss is good.
△: there are some irregular places on the surface, and gloss is poor slightly.
*: there are quite a lot of irregular place, gloss difference in the surface.
(9) drawdown: the resin combination pellet is shaped to the 100mm square plate, and its thickness is 1.5mm, carries out fastening location with the anchor clamps that have the 76mm square aperture then, measures the drawdown of this sheet in 30 minutes in 190 ℃ baking oven.
(10) evaluation of expanded molded article: in 100 parts of resin combination pellets, add 1.0 parts of Cellmic C 121s (whipping agent), and carry out injection molding and make expanded molded article, and the situation of the cross section chamber of this expanded molded article is carried out the naked eyes evaluation.
Zero: tiny and even.
△: have ununiformity to a certain degree.
*: inhomogeneous.
(11) situation of foam sheet: by observing the surface appearance of estimating foam sheet and cross section thereof.
Zero: the place of no surface imperfection or successive bubble present uniform situation generally.
*: the irregular place of squamous is arranged from the teeth outwards or be the place of ripple, perhaps have the part of open-celled structure, be inhomogeneous situation generally.
(12) rolling temperature scope: use the two rollers (stack) of diameter as 15.24cm, its condition is that the surface temperature of roller is 160～230 ℃, roller speed is 10m/min (the roller speed ratio is 1: 1.1), the spacing of roller is 0.3mm, the 100g sample was placed on the roller roll-in 5 minutes, pull out the sheet material that makes, determine to obtain the temperature range of satisfied sheet material.
(13) drawability: in the calendering of above-mentioned (12), estimate roll release performance and surface quality.
The roll release performance
Zero: get final product roll release without any obstruction.
△: exist during roll release and hinder.
*: be difficult to pull out sheet material from roller.
Surface quality
Zero: no coarse.
△: have tiny coarse part.
*: there is bigger coarse part.
(14) ooze out performance: with the thick compressing tablet of sheet preparation 1mm that obtains in above-mentioned (12), make it in 60 ℃ oven heat, place a week after, estimate the degree of oozing out of sheet surface.
Zero: no any oozing out.
△: have some to ooze out.
*: oozing out of certain degree arranged.
(15) total light transmittance of sheet material, mist degree and gloss (45 ° of gloss): measure these performances with the described method of JIS K7105.
(16) the plastic temperature range of sheet material: use air-pressure forming machine (FBP-M2 (trade mark) that CDK Co. produces) with constant compression force formed sheet (diameter: 10mm, highly: 6mm), determine to obtain the desirable plastic temperature range of the uniform moulded products of general thickness.
Reference example 1
The preparation of polymethyl acrylic acid dodecyl ester dispersion of polymer particle (B-1)
Dissolving is 0.1 part 2 in the mixing solutions of 50 parts of lauryl methacrylates and 50 parts of methyl methacrylates, 2 '-azo two (2, the 4-methyl pentane nitrile).In this solution, add the mixing solutions that contains 2.0 parts of Sodium dodecylbenzene sulfonatees and 300 parts of distilled water then, under 10000rpm, stir after 2 minutes, make its process homogenizer twice under 30MPa pressure, obtain stable primary dispersion body with uniform mixer.This dispersion is joined in another flask of being furnished with stirring arm, condenser, thermopair and nitrogen inlet, under nitrogen gas stream, internal temperature is risen to 80 ℃, and this mixture stirred carried out radical polymerization in 3 hours, obtain dispersion of polymer particle (hereinafter referred to as " B-1 ").
The solids concn of B-1 is 25.1%, and size distribution presents unimodal, and weight average particle diameter is 191nm, and surface potential is-58mV.
Reference example 2
The preparation of polymethyl acrylic acid dodecyl ester dispersion of polymer particle (B-2)
Obtain dispersion of polymer particle (hereinafter referred to as " B-2 ") in the mode identical with reference example 1, different is to replace 50 parts of methyl methacrylates with 50 parts of vinylbenzene.
The solids concn of B-2 is 25.2%, and size distribution presents unimodal, and weight average particle diameter is 178nm, and surface potential is-61mV.
Reference example 3
The preparation of polyolefin resin melt tension toughener (C-1)
The Fluon AD936 that produces with Asahi ICI Fluoropolymers is as the polytetrafluoroethylparticle particle dispersion.The solids concn of Fluon AD936 is 63.0%, and with respect to tetrafluoroethylene, it contains 5% polyoxyethylene alkyl phenyl ether.The size distribution of Fluon AD936 presents unimodal, and weight average particle diameter is 290nm, and surface potential is-20mV.
Add 116.7 parts of distilled water in 83.3 parts of Fluon AD936, obtain polytetrafluoroethylparticle particle dispersion A-1, its solids concn is 26.2%.A-1 contains 25% tetrafluoroethylene and 1.2% polyoxyethylene alkyl phenyl ether.
To another be furnished with add 120 parts of A-1 (30 parts of tetrafluoroethylene) and 199.2 parts of B-1 (50 parts of lauryl methacrylate/methylmethacrylate copolymers) in the flask of stirring arm, condenser, thermopair and nitrogen inlet after, under the nitrogen gas stream in this mixture of stirring at room 1 hour.Internal temperature is risen to 80 ℃ then, keep this temperature after 1 hour, the mixing solutions that adds 0.001 part of ferrous sulfate (II), 0.003 part of disodium ethylene diamine tetraacetate, 0.24 portion of Rongalite salt and 60.8 parts of distilled water, in 1 hour, be added dropwise to the mixing solutions of 20 parts of methyl methacrylates and 0.4 part of tert-butyl peroxide then, be added dropwise to complete the back keep internal temperature 80 ℃ 1 hour, to finish radical polymerization.In this process, find no solid and isolate, obtain uniform particle dispersion.
90 ℃ down are incorporated into this particle dispersion in 400 parts of hot water that contain 5 parts of calcium chloride, to isolate solid part, filter and drying after obtain 98 parts of polyolefin resin melt tension toughener powder (hereinafter referred to as " C-1 ").
Table 1 has been listed A-1, B-1 used in above-mentioned and the amount of dropping polymeric methyl methacrylate.
Reference example 4 and 5
The preparation of polyolefin resin melt tension toughener (C-2 and C-3)
Obtain polyolefin resin melt tension toughener C-2 and C-3 in the mode identical with reference example 3, the amount such as the table 1 of different is A-1, B-1 and dropping polymeric methyl methacrylate are listed.
Table 1
| The amount of A-1 (part) | The amount of B-1 (part) | The amount of MMA (part) | |
| C-1 | 120 | 199.2 | 20 |
| C-2 | 80 | 239.0 | 20 |
| C-3 | 40 | 278.9 | 20 |
Reference example 6
The preparation of polyolefin resin melt tension toughener (C-4)
Prepare polyolefin resin melt tension toughener powder (hereinafter referred to as " C-4 ") in the mode identical with reference example 3, different is to replace 199.2 parts of B-1 with 198.4 parts of B-2.
Reference example 7
The preparation of polyolefin resin melt tension toughener (C-5)
To another be furnished with add 120 parts of A-1 (30 parts of tetrafluoroethylene) and 277.8 parts of B-2 (70 parts of lauryl methacrylate/styrol copolymers) in the flask of stirring arm, condenser, thermopair and nitrogen inlet after, under the nitrogen gas stream in this mixture of stirring at room 1 hour.Internal temperature is risen to 80 ℃ then, kept this temperature 1 hour.In this process, find no solid and isolate, obtain uniform particle dispersion.
90 ℃ down are incorporated into this particle dispersion in 400 parts of hot water that contain 5 parts of calcium chloride, to isolate solid part, filter and drying after obtain 99 parts of polyolefin resin melt tension toughener powder (hereinafter referred to as " C-5 ").
Reference example 8
The preparation of polyolefin resin melt tension toughener (C-6)
With 50 parts of MFR homopolymer polypropylene (hereinafter referred to as " PP-1 ") pellet that is 5.0g/10min with after the melt tension toughener C-2 of 50 parts of preparations in reference example 4 mix, usefulness twin screw extruder (WERNER ﹠amp; The ZSK30 (trade mark) that PFLEIDERER produces) carry out melt kneading, barrel zone temperature is 200 ℃, and screw speed is 200rpm, obtains the melt tension toughener (hereinafter referred to as " C-6 ") of pellet form.
Listed the composition of the melt tension toughener C-1 to C-6 that in reference example 3～8, obtains in the table 2.
Table 2
| The melt tension toughener | Form (%) | |||
| Component (A) | Monomer constitutes component (B) | Polymeric monomer in the presence of A, B | Polyolefine | |
| C-1 C-2 C-3 C-4 C-5 C-6 | PTFE(30) PTFE(20) PTFE(10) PTFE(30) PTFE(30) PTFE(10) | DMA(25)/MMA(25) DMA(30)/MMA(30) DMA(35)/MMA(35) DMA(25)/ST(25) DMA(35)/ST(35) MDA(15)/MMA(15) | MMA(20) MMA(20) MMA(20) MMA(20) MMA(10) | PP-1(50) |
PTFE: tetrafluoroethylene
DMA: lauryl methacrylate
MMA: methyl methacrylate
ST: vinylbenzene
PP-1: melt flow rate (MFR) is the homopolymer polypropylene of 5.0g/10min
Embodiment 1～8
With homopolymer polypropylene pellet P-1 (melt flow rate (MFR): 5.0g/10min) as polyolefin resin, and with in the reference example 3～8 preparation melt tension toughener C-1 to C-6 go into wherein with the listed ratio hand mix of table 3, use twin screw extruder (WERNER ﹠amp afterwards; The ZSK30 that PFLEIDERER produces) carry out melt kneading, barrel zone temperature is 200 ℃, and screw speed is 200rpm, forms pellet.The performance of measuring the gained pellet is also with the results are shown in Table 3.
Comparative Examples 1～4
For the purpose of contrast, under the condition identical, obtain pellet (Comparative Examples 1) by the extruded polyolefin resin with embodiment 1, by powder mix powder tetrafluoroethylene and powder polyolefine, with Henschel mixing tank this mixture of high-speed stirring at room temperature, in mixing process, apply shearing force so that tetrafluoroethylene becomes fibrous, under the condition identical, extrude then, obtain pellet (Comparative Examples 2～4) thus, estimate in the mode identical with embodiment 1 with embodiment 1.The results are shown in Table 3.
As polyolefin resin, the Fluon CD123 that produces with Asahi ICI Fluoropolymers is as powdery polytetrafluoroethylene teflon with homopolymer polypropylene pellet P-1 (Comparative Examples 1) or Powdered polypropylene P-2 (Comparative Examples 2～4) (melt flow rate (MFR) of the two is 5.0g/10min).CD123 is made of the tetrafluoroethylene primary particle, and its particle diameter is 0.2～0.3 μ m, is condensed into the condensation product of hundreds of μ m size.
Table 3
| Form (part) | PTFE in the composition (%) | MT (g ) | SR | MFR(g /10mi n) | Young's modulus (MPa) | The outward appearance of roll-in sheet material | Drawdown (mm) | The evaluation of expanded molded article | ||
| Polyolefin resin | The melt tension toughener | |||||||||
| Embodiment 12345678 17 Comparative Examples 1234 | P-1(100) P-1(100) P-1(100) P-1(100) P-1(100) P-1(100) P-1(100) P-1(100) P-1(100) P-1(100) P-2(100) P-2(100) P-2(100) | The no CD123 of C-1 (5) C-1 (3) C-1 (1) C-2 (4.5) C-3 (9.9) C-4 (3) C-5 (3) C-6 (9.9) C-7 (4.5) (0.3) CD123 (0.9) CD123 (1.5) | 1.43 0.87 0.30 0.86 0.90 0.87 0.87 0.90 0.86 0 0.30 0.89 1.48 | 28 19 9 19 19 19 20 18 18 3 3 4 5 | 2.4 2.1 2.0 2.1 2.2 2.2 2.3 2.2 2.1 1.3 1.3 1.3 1.4 | 1.9 3.2 4.2 3.1 3.2 3.1 3.1 3.3 3.0 5.0 4.0 3.5 3.0 | 1370 1350 1350 1350 1350 1350 1350 1350 1350 1350 1350 1350 1350 | ○ ○ ○ ○ ○ ○ △ ○ ○ ○ × × × | 0 0 2 0 0 0 0 0 0 90 62 51 41 | ○ ○ △ ○ ○ ○ ○ ○ ○ × × × × |
P-1: homopolymer polypropylene pellet (melt flow rate (MFR): 5.0g/10min)
P-2: Powdered polypropylene (melt flow rate (MFR): 5.0g/10min)
CD123: powdery polytetrafluoroethylene teflon (by the FluonCD123 of Asahi ICI Fluoropolymers production)
MT: melt tension
SR: ratio of expansion
MFR: melt flow rate (MFR)
Compare with the Comparative Examples that contains same amount PTFE, the composition that contains melt tension toughener of the present invention has melt tension value and the ratio of expansion that significantly improves, this is the sign explanation of drawing-off performance, hot formability, blow molding and the foaming of calendering, has confirmed that thus it can provide gratifying moulding processability.Also demonstrate on the other hand, melt flow rate (MFR) reduces less, and the performance undamaged mistake of extrusion moulding.Same extraordinary outward appearance, drawdown and the foaming that also has the roll-in sheet material.
Embodiment 9～11
(melt flow rate (MFR): 5.0g/10min) (melt flow rate (MFR): mixture 0.3g/10min) is as polyolefine with new LDPE (film grade) pellet E-1 with homopolymer polypropylene pellet P-1, and with in the reference example 3 preparation melt tension toughener C-1 go into wherein with the listed ratio hand mix of table 4, form pellet in the mode identical afterwards with embodiment.The performance of measuring the gained pellet is also with the results are shown in Table 4.
Comparative Examples 6～11
By extruding homopolymer polypropylene pellet P-1 and new LDPE (film grade) pellet E-2 (Comparative Examples 6～8) obtains pellet, by mixed powder polypropylene P-2, powder new LDPE (film grade) E-2 (melt flow rate (MFR): 0.3g/10min) with the powder tetrafluoroethylene, mix with the Henschel mixing tank, extrude then, obtain pellet (Comparative Examples 9～11), these two kinds of pellets are estimated in the mode identical with embodiment 1.The results are shown in Table 4.
Table 4
| Form (part) | PTFE in the composition (%) | MT (g) | SR | MFR(g /10mi n) | Young's modulus (MPa) | The outward appearance of roll-in sheet material | Drawdown (mm) | The evaluation of expanded molded article | ||
| Polyolefin resin | The melt tension toughener | |||||||||
| Embodiment 9 10 11 Comparative Examples 6789 10 11 | P-1(100)，E-1(20) P-1(100)，E-1(50) P-1(100)，E-1(100) P-1(100)，E-1(20) P-1(100)，E-1(50) P-1(100)，E-1(100) P-2(100)，E-2(20) P-2(100)，E-2(50) P-2(100)，E-2(100) | C-1(2.5) C-1(3.1) C-1(4.2) CD123(0.8) CD123(1.0) CD123(1.3) | 0.61 0.61 0.62 0 0 0 0.66 0.66 0.65 | 20 26 39 3 4 6 4 5 8 | 2.1 2.2 2.3 1.3 1.4 1.5 1.4 1.6 1.6 | 3.2 3.4 3.5 5.0 5.0 5.0 3.0 3.2 3.3 | 1200 900 700 1200 900 700 1200 900 700 | ○ ○ ○ ○ ○ ○ × × × | 0 0 0 40 30 30 20 20 10 | ○ ○ ○ × × × × × × |
P-1: homopolymer polypropylene pellet (melt flow rate (MFR): 5.0g/10min)
P-2: powder polypropylene (melt flow rate (MFR): 5.0g/10min)
E-1: new LDPE (film grade) pellet (melt flow rate (MFR): 0.3g/10min)
E-2: powder polyethylene (melt flow rate (MFR) 0.3g/10min)
CD123: powdery polytetrafluoroethylene teflon
MT: melt tension
SR: ratio of expansion
MFR: melt flow rate (MFR)
Embodiment 12～13
With the listed ratio of table 5, hand mix homopolymer polypropylene pellet P-1 (melt flow rate (MFR): 5.0g/10min), new LDPE (film grade) pellet E-1 (melt flow rate (MFR): 0.3g/10min), the melt tension toughener C-1 that makes in the reference example 3 and carry out light calcium carbonate that the surface-treated particle diameter is 0.15 μ m with lipid acid after, obtain pellet in the mode identical with embodiment 1.The performance of measuring the gained pellet is also with the results are shown in Table 5.
Comparative Examples 12～15
In the mode identical with embodiment 1, with table 5 the ratio of class by hand mix homopolymer polypropylene pellet P-1 (melt flow rate (MFR): 5.0g/10min), new LDPE (film grade) pellet E-1 (melt flow rate (MFR): 0.3g/10min) and with lipid acid carry out the light calcium carbonate that the surface-treated particle diameter is 0.15 μ m, obtain pellet (Comparative Examples 12～13), pass through mixed powder polypropylene P-2 with the ratio that table 5 is listed, powder new LDPE (film grade) E-2 (melt flow rate (MFR): 0.3g/10min), carry out light calcium carbonate and the powder tetrafluoroethylene that the surface-treated particle diameter is 0.15 μ m with lipid acid, mix with the Henschel mixing tank, extrude then, obtain pellet (Comparative Examples 14～15), in the mode identical these two kinds of pellets are estimated with embodiment 1, measure its performance, and with the results are shown in Table 5.
Table 5
| Form (part) | PTFE. in the composition (%) | MT (g) | SR | MFR(g /10mi n) | Young's modulus (MPa) | The outward appearance of roll-in sheet material | Drawdown (mm) | |||
| Polyolefin resin | Lime carbonate | The melt tension toughener | ||||||||
| Embodiment 12 13 Comparative Examples 12 13 14 15 | P-1(100) P-1(100)，E-1(50) P-1(100) P-1(100)，E-1(50) P-2(100) P-2(100)，E-2(50) | (50) (50) (50) (50) (50) (50) | C-1(2.5) C-1(3.3) 0 0 CD123(0.8) CD123(1.0) | 0.49 0.49 0 0 0.53 0.50 | 26 28 4 4 5 5 | 2.2 2.3 1.3 1.4 1.5 1.6 | 3.2 3.3 5.0 5.0 3.0 3.2 | 1600 1100 1600 1100 1600 1100 | ○ ○ ○ ○ × × | 0 0 90 30 30 20 |
P-1: homopolymer polypropylene pellet (melt flow rate (MFR): 5.0g/10min)
P-2: powder polypropylene (melt flow rate (MFR): 5.0g/10min)
E-1: new LDPE (film grade) pellet (melt flow rate (MFR) 0.3g/10min)
E-2: powder polyethylene (melt flow rate (MFR) 0.3g/10min)
CD123: powdery polytetrafluoroethylene teflon
Lime carbonate: particle diameter is the light calcium carbonate of 0.15 μ m, carries out surface treatment with lipid acid
MT: melt tension
SR: ratio of expansion
MFR: melt flow rate (MFR)
Embodiment 14～16
Carry out new LDPE (film grade) (LLDPE) pellet E-3 (melt flow rate (MFR): that polymerization obtains with the use metallocene catalyst 2.6g/10min) as polyolefin resin, the melt tension toughener C-1 that itself and reference example 3 are made, carry out hand mix with the ratio that table 6 is listed, use twin screw extruder (WERNER ﹠amp afterwards; The ZSK30 that PFLEIDERER produces) carry out melt kneading, barrel zone temperature is 200 ℃, and screw speed is 200rpm, forms pellet.Measure the performance of gained pellet, and with the results are shown in Table 6.
Comparative Examples 16
For the purpose of contrast, by E-3 is extruded into pellet under the condition identical with embodiment 1, and then once under the condition identical, extrude with embodiment 1, obtain pellet, in the mode identical this pellet is estimated with embodiment 1.The results are shown in Table 6.
Table 6
| Form (part) | PTFE in the composition (%) | MT(g) | SR | MFR (g/10min) | Roll-in sheet material outward appearance | ||
| Polyolefin resin | The melt tension toughener | ||||||
| Embodiment 14 15 16 Comparative Examples 16 | E-3(100) E-3(100) E-3(100) E-3(100) | C-1 (5) C-1 (3) C-1 (1) does not have | 1.43 0.87 0.30 0 | 2 17 8 2 | 2.3 2.1 2.0 1.3 | 1.2 1.7 1.9 2.0 | ○ ○ ○ ○ |
E-3: with metallocene catalyst synthetic new LDPE (film grade) pellet (MFR2.0g/10min)
MT: melt tension
SR: ratio of expansion
MFR: melt flow rate (MFR)
Reference example 9
The preparation of polyolefin resin melt tension toughener (C-7)
After in the flask of being furnished with stirring arm, condenser, thermopair and nitrogen inlet, adding 0.6 part of Sodium dodecylbenzene sulfonate and 115 parts of distilled water, under nitrogen gas stream, temperature is risen to 80 ℃.The mixing solutions that adds 0.00024 part of ferrous sulfate (II), 0.00072 part of disodium ethylene diamine tetraacetate, 0.29 portion of Rongalite salt and 5 parts of distilled water then at blended simultaneously, and internal temperature risen to 80 ℃, in 3 hours, be added dropwise to the mixing solutions of 42 parts of methacrylic acid 2-ethylhexyls, 18 parts of methyl methacrylates and 0.12 part of cumene hydroperoxide afterwards, to impel radical polymerization.After dropwising, kept 80 ℃ of internal temperatures 1 hour, be sequentially added into 33.33 parts of AD936 (20 parts of tetrafluoroethylene) and 51.37 parts of distilled water afterwards, and with internal temperature remain on 80 ℃ 1 hour.Next the mixing solutions that adds 1 part of Witco 1298 Soft Acid and 13 parts of distilled water, internal temperature is transferred to 80 ℃, in 30 minutes, drip the mixing solutions of 20 parts of methyl methacrylates and 0.04 part of tert-butyl peroxide, after being added dropwise to complete temperature remained on 80 ℃ 1 hour, to finish radical polymerization.In this process, do not find to isolate solid, obtain uniform particle dispersion.90 ℃ down are incorporated into this particle dispersion in 400 parts of hot water that contain 5 parts of calcium chloride, to isolate solid part, filter and drying after obtain 98 parts of polyolefin resin melt tension toughener powder (hereinafter referred to as " C-7 ").
Embodiment 17
With C-7 replaced C-2, estimate the effect that adds C-7 in the mode identical with embodiment 4.
The results are shown in Table 3.
The composition that contains melt tension toughener of the present invention has melt tension value and the ratio of expansion that significantly improves, this is the sign explanation of drawing-off performance, hot formability, blow molding and the foaming of calendering, has confirmed that thus it can provide gratifying moulding processability.Also demonstrate on the other hand, melt flow rate (MFR) reduces less, and the performance undamaged mistake of extrusion moulding.The same extraordinary outward appearance that also has the roll-in sheet material.
Embodiment 18
Use is by Nihon Polychem, KK. the homopolymer polypropylene pellet EA9 (trade mark of Sheng Chaning, melt flow rate (MFR): 0.5g/10min) as polyolefin resin, and estimating the outward appearance of its melt tension, ratio of expansion, melt flow rate (MFR), Young's modulus and roll-in sheet material, the result who obtains lists in the table 7 with " untapped sample ".After the melt tension toughener C-1 that makes in 0.2 part of reference example 3 joins the test piece of the 100 weight parts crushing that untapped sample obtains by compression moulding with the form of hand mix, with twin screw extruder (WERNER ﹠amp; The ZSK30 that PFLEIDERER produces) carry out melt kneading, barrel zone temperature is 200 ℃, and screw speed is 200rpm, forms pellet.The pellet of gained is labeled as regeneration goods a1.Estimate the performance of these regeneration goods a1.Then, the melt tension toughener C-1 that makes in 0.2 part of reference example 3 is joined the test piece of the crushing that 100 weight parts obtain by compression moulding regeneration goods a1, and with the mode identical with regeneration goods a1 obtain the regenerating pellet of goods a2.Estimate the performance of these regeneration goods a2.Obtain the pellet of goods a3 of regenerating by regeneration goods a2 in an identical manner, and estimate its performance.Regeneration goods a1～a3 estimated the results are shown in Table 7.
Table 7
| MT(g) | SR | MFR | Young's modulus (MPa) | The outward appearance of roll-in sheet material | |
| Untapped sample | 14 | 1.3 | 0.5 | 1300 | ○ |
| Regeneration sample a1 | 14 | 1.3 | 0.5 | 1300 | ○ |
| Regeneration sample a2 | 14 | 1.3 | 0.5 | 1300 | ○ |
| Regeneration sample a3 | 14 | 1.3 | 0.5 | 1300 | ○ |
Comparative Examples 17
For the purpose of contrast, under the situation that does not add melt tension toughener C-1, obtain the pellet of goods b1～b3 of regenerating in the mode identical, and estimate their performance with embodiment 18.The results are shown in Table 8.
Table 8
| MT(g) | SR | MFR | Young's modulus (MPa) | The outward appearance of roll-in sheet material | |
| Regeneration sample b1 | 12 | 1.3 | 0.6 | 1300 | ○ |
| Regeneration sample b2 | 9 | 1.2 | 0.7 | 1300 | ○ |
| Regeneration sample b3 | 7 | 1.2 | 0.8 | 1300 | ○ |
Comparative Examples 18
For the purpose of contrast, use 0.2 part of powder tetrafluoroethylene to replace melt tension toughener C-1 of the present invention, with the mode identical obtain the regenerating pellet of goods c1～c3 with embodiment 1.Their performance estimated the results are shown in Table 9.Here the Fluon CD123 (trade mark) that uses Asahi ICIFluoropolymers production is as the powder tetrafluoroethylene.
Table 9
| MT(g) | SR | MFR | Young's modulus (MPa) | The outward appearance of roll-in sheet material | |
| Regeneration sample c1 | 11 | 1.3 | 0.6 | 1300 | × |
| Regeneration sample c2 | 10 | 1.2 | 0.7 | 1300 | × |
| Regeneration sample c3 | 8 | 1.2 | 0.8 | 1300 | × |
In table 7～9, MT: melt tension, SR: ratio of expansion, MFR: melt flow rate (MFR)
The composition that contains melt tension toughener of the present invention does not have the change on any performance extremely, it is typically the lower melt tension when regeneration, they are proved has gratifying calendering stretchiness, hot formability, blow molding and foaming, is similar to original product.The outward appearance of composition also is gratifying.
Reference example 10
The preparation of polyolefin resin melt tension toughener (C-8)
With 0.1 part 2,2 '-azo two (2, the 4-methyl pentane nitrile) is dissolved in 100 parts of lauryl methacrylates.The mixture that adds 2.0 parts of Sodium dodecylbenzene sulfonatees and 300 parts of distilled water then, and stirred 2 minutes with the rotating speed of 10000rpm with homogenizer, make it under the pressure of 30MPa, pass through homogenizer twice, obtain the primary dispersion body of stable lauryl methacrylate.It is joined be furnished with stirring arm, in another flask of condenser, thermopair and nitrogen inlet, make its internal temperature rise to 80 ℃ under the nitrogen gas stream, and this mixture kept 80 ℃ and stirred 3 hours at internal temperature under nitrogen gas stream, to carry out radical polymerization, obtain the dispersion of polymer particle (hereinafter referred to as " B-3 ") of lauryl methacrylate.
The solids concn of B-3 is 25.2%, and size distribution presents unimodal, and weight average particle diameter is 195nm, and surface potential is-38mV.
To another be furnished with add the A-1 (20 parts of tetrafluoroethylene) and 198.4 parts of B-3 (50 parts of polymethyl acrylic acid dodecyl esters) that obtains in 80 parts of reference examples 3 in the flask of stirring arm, condenser, thermopair, nitrogen inlet and dropping funnel after, under the nitrogen gas stream this mixture was stirred under room temperature 1 hour.Internal temperature is risen to 80 ℃ then, after adding the mixing solutions of 0.001 part of ferrous sulfate (II), 0.003 part of disodium ethylene diamine tetraacetate, 0.24 portion of Rongalite salt and 10 parts of deionized waters, in 1 hour, be added dropwise to the mixing solutions of 30 parts of methyl methacrylates and 0.6 part of tert-butyl peroxide, be added dropwise to complete the back keep internal temperature 80 ℃ 1 hour, to finish radical polymerization.In this process, find no solid and isolate, obtain uniform particle dispersion.The solids concn of this particle dispersion is 31.3%, and the relative broad of size distribution, its weight average particle diameter are 252nm.
Under 70 ℃ 319.5 parts of these particle dispersions are incorporated in 600 parts of hot water that contain 5 parts of calcium chloride, to isolate solid part, filter and drying after obtain 99 parts of polyolefin resin melt tension tougheners (hereinafter referred to as " C-8 ").
Under 220 ℃, exsiccant C-8 is shaped to band shape with compaction forming machine, is made into ultrathin section with slicing machine then, need not dye it is observed with transmission electron microscope.Observed tetrafluoroethylene is the part of obfuscation, but does not observe the aggregate that surpasses 10 μ m.
Embodiment 19～21, Comparative Examples 19～21
Use linear polypropylene homopolymer pellet (melt flow rate (MFR): 5.0g/10min) as polyolefin resin, and with the polyolefin resin melt tension toughener (C-8) that obtains in the reference example 10, whipping agent (Trimethylmethane) and bubble conditioning agent (talcum) and its are at forcing machine (screw diameter: 50mm, L/D=46) mix in, carry out melt kneading with the ratio that table 10 is listed, afterwards this mixture is extruded, and under the listed blowing temperature of table 10, make its foaming for tubular, the circular port mould of 75mm φ (port mould diameter) wherein is installed on the forcing machine end, the mouth die clearance is 0.3mm (die lip gap), pull it simultaneously, make the internal surface and cooling core rod (core rod diameter: 200mm) contact of tubular foam, then tubular foam is cut open along extruding direction, obtained sheet material.The situation of extrusion condition and each gained foam sheet is listed in the table 10.
For the purpose of contrast, the forming composition (Comparative Examples 21) of not adding the extrusion moulding thing (Comparative Examples 19) that contains the teflon mixture powder, being added with the tetrafluoroethylene fine powder forming composition (Comparative Examples 20) of (the Fluon CD123 that is produced by Asahi ICI Fluoropolymers) and only being added with the bubble conditioning agent is estimated in an identical manner.The results are shown in Table 10.
Table 10
| Blending ratio (%) | Blowing temperature (℃) | Evaluation to foam sheet | |||||||
| PP | C-8 | CD123 | Whipping agent | The bubble conditioning agent | Density (g/cm 3) | Thickness (mm) | Situation | ||
| Embodiment 19 | 85 | 5 | 0 | 10 | 0 | 156 | 0.058 | 1.7 | ○ |
| 20 | 90 | 5 | 0 | 5 | 0 | 157 | 0.098 | 1.5 | ○ |
| 21 | 84.9 | 5 | 0 | 10 | 0.1 | 156 | 0.056 | 1.6 | ○ |
| Comparative Examples 19 | 90 | 0 | 0 | 10 | 0 | 157 | 0.062 | 1.7 | × |
| 20 | 88 | 0 | 2 | 10 | 0 | 157 | 0.060 | 1.7 | × |
| 21 | 89.9 | 0 | 0 | 10 | 0.1 | 158 | 0.061 | 1.5 | × |
PP: homopolymer polypropylene pellet (melt flow rate (MFR) 0.5g/min)
CD123: fine polytetrafluoroethylpowder powder end (by the FluonCD123 of Asahi ICI Fluoropolymers production)
Reference example 11
The preparation of polyolefin resin melt tension toughener (C-9)
Dissolving is 0.1 part 2 in the mixing solutions of 75 parts of lauryl methacrylates and 25 parts of methyl methacrylates, 2 '-azo two (2, the 4-methyl pentane nitrile).Then to wherein adding the mixing solutions that contains 2.0 parts of Sodium dodecylbenzene sulfonatees and 300 parts of distilled water, stirred 4 minutes under 10000rpm with homogenizer afterwards, make it under the pressure of 30MPa, pass through homogenizer twice, obtain the primary dispersion body of stable lauryl methacrylate/methyl methacrylate.It is joined be furnished with stirring arm, in another flask of condenser, thermopair and nitrogen inlet, make its internal temperature rise to 80 ℃ under the nitrogen gas stream, and this mixture kept 80 ℃ and stirred 3 hours at internal temperature under nitrogen gas stream, to carry out radical polymerization, obtain the copolymer particle dispersion (hereinafter referred to as " B-4 ") of lauryl methacrylate/methyl methacrylate.
The solids concn of B-4 is 25.1%, and size distribution presents unimodal, and weight average particle diameter is 198nm, and surface potential is-39mV.
To another be furnished with add the A-1 (40 parts of tetrafluoroethylene) and 159.4 parts of B-4 (multipolymers of 40 parts of lauryl methacrylate/methyl methacrylates) that obtains in 160 parts of reference examples 3 in the flask of stirring arm, condenser, thermopair, nitrogen inlet and dropping funnel after, under the nitrogen gas stream this mixture was stirred under room temperature 1 hour.Internal temperature is risen to 80 ℃ then, after adding the mixing solutions of 0.001 part of ferrous sulfate (II), 0.003 part of disodium ethylene diamine tetraacetate, 0.24 portion of Rongalite salt and 10 parts of distilled water, in 30 minutes, be added dropwise to the mixing solutions of 20 parts of methyl methacrylates and 0.1 part of tert-butyl peroxide, be added dropwise to complete the back keep internal temperature 80 ℃ 1 hour, to finish radical polymerization.In this process, find no solid and isolate, obtain uniform particle dispersion.The solids concn of this particle dispersion is 28.5%, and the relative broad of size distribution, its weight average particle diameter are 248nm.
Under 75 ℃ 349.7 parts of these particle dispersions are incorporated in 600 parts of hot water that contain 5 parts of calcium chloride, to isolate solid part, filter and drying after obtain 97 parts of polyolefin resin melt tension tougheners (hereinafter referred to as " C-9 ").
Under 220 ℃, exsiccant C-9 is shaped to band shape with compaction forming machine, is made into ultrathin section with slicing machine then, need not dye it is observed with transmission electron microscope.Observed tetrafluoroethylene is the part of obfuscation, does not observe the aggregate that surpasses 10 μ m.
Embodiment 22, Comparative Examples 22～26
With the C-9 that obtains in the reference example 11 and the 100 parts of linear polypropylene homopolymer pellets (EA9 that produces by Nihon Polychem, melt flow rate (MFR): 0.5g/10min) mix, blending ratio is listed in the table 12, and this mixture is extruded under 230 ℃ with forcing machine, makes pellet.Carry out calendering formation with this pellet, the performance of the temperature range of calendering formation, calendering formation thing and sheet material are oozed out estimate.The results are shown in Table 12.
For the purpose of contrast, with do not add the extrusion moulding thing (Comparative Examples 22) that contains the teflon mixture powder, be added with the tetrafluoroethylene fine powder forming composition (Comparative Examples 23,24) of (the Fluon CD123 that produces by Asahi ICI Fluoropolymers), the forming composition (Comparative Examples 26) that is added with the forming composition (Comparative Examples 25) of granulated glass sphere (GB731MC (trade mark) that ToshibaBallotini produces) and is added with metallic soap (lithium stearate) is estimated in an identical manner.The results are shown in Table 12.
Embodiment 23-28
Prepare pellet in the mode identical with embodiment 22, different is to replace 100 parts of linear polypropylene homopolymer pellets (by the EA9 of Nihon Polychem production with 100 parts of each resins of listing in the table 11, melt flow rate (MFR): 0.5g/10min), and in an identical manner these are estimated.The results are shown in Table 12.
Table 11
| Used resin | MFR (g/10min) | Product | |
| Embodiment 23 | The propylene and ethylene segmented copolymer | 0.5 | EA9，Nippon Polychem |
| 24 | Contain the above-mentioned resin of 30% steatitic | 0.1 | The EA9/ talcum |
| 25 | The propylene and ethylene random copolymers | 3.0 | SPX9600 (trade mark), Nippon Polychem |
| 26 | High density polyethylene(HDPE) | 0.3 | HDBZ50U (trade mark), Nippon Polychem |
| 27 | New LDPE (film grade) | 8.0 | LC602A (trade mark), Nippon Polychem |
| 28 | Ethylene-vinyl acetate copolymer | 15 | LV670 (trade mark), Nippon Polychem |
Table 12
| Resin | Additive | The rolling temperature scope (℃) | The calendering formation performance | Ooze out | |||
| Type | Amount (part) | Demolding performace | Surface quality | ||||
| Embodiment 22 | EA9 | C-9 | 0.25 | 22 | ○ | ○ | ○ |
| Comparative Examples 22 | EA9 | 2 | × | ○ | ○ | ||
| 23 | EA9 | CD123 | 0.1 | 3 | × | × | ○ |
| 24 | EA9 | CD123 | 1.0 | 3 | △ | × | ○ |
| 25 | EA9 | Granulated glass sphere | 1.0 | 9 | △ | × | ○ |
| 26 | EA9 | Metallic soap | 1.0 | 2 | ○ | ○ | △ |
| Embodiment 23 | EC9 | C-9 | 0.25 | 23 | ○ | ○ | ○ |
| 24 | The EC9/ talcum | C-9 | 0.25 | 23 | ○ | ○ | ○ |
| 25 | SPX9600 | C-9 | 0.25 | 22 | ○ | ○ | ○ |
| 26 | HDBZ50U | C-9 | 0.25 | 21 | ○ | ○ | ○ |
| 27 | LC602A | C-9 | 0.25 | 26 | ○ | ○ | ○ |
| 28 | LV670 | C-9 | 0.25 | 19 | ○ | ○ | ○ |
Embodiment 29
With the linear polypropylene homopolymer pellet (EA7 (trade mark) that produces by Nippon Polychem, melt flow rate (MFR): 1.2g/10min) with the C-9 of reference example 11 gained, mix with the ratio that table 13 is listed, and with the single screw extrusion machine that T mouth mould is installed (screw diameter: 50mm, L/D=28) under 230 ℃, 50rpm, this mixture is mediated, extruded and obtain the thermoforming polyolefin sheets that thickness is 0.3mm.Total light transmittance, mist degree and plastic temperature range to resulting sheet are estimated, and with the results are shown in Table 13.
For the purpose of contrast, the forming composition (Comparative Examples 28 and 29) that does not add the extrusion moulding thing (Comparative Examples 27) of C-9 and be added with fine polytetrafluoroethylpowder powder end (by the Fluon CD123 of Asahi ICI Fluoropolymers production) is estimated in an identical manner.The results are shown in Table 13.
Table 13
| Form (weight part) | Embodiment | Comparative Examples | ||
| 29 | 27 | 28 | 29 | |
| PP | 100 | 100 | 100 | 100 |
| C-9 | 0.25 | |||
| CD123 | 0.1 | 1.0 | ||
| Total light transmittance | 90 | 88 | 86 | 71 |
| Mist degree (%) | 22 | 26 | 40 | 42 |
| Gloss (%) | 100 | 100 | 65 | 59 |
| Plastic temperature range (℃) | 18 | 2 | 3 | 3 |
Embodiment 30, Comparative Examples 30～32
With linear polypropylene homopolymer pellet (by the EA7 that Nippon Polychem produces, melt flow rate (MFR): 1.2g/10min), the C-9 of talcum and reference example 11 gained, mix with the ratio that table 14 is listed, with twin screw extruder (WERNER ﹠amp; The ZSK30 that PFLEIDERER produces) carry out melt kneading, barrel zone temperature is 200 ℃, and screw speed is 200rpm, forms pellet.(screw diameter: 50mm L/D=28) mediates this mixture under 230 ℃, 50rpm, extrudes and obtains the thermoforming polyolefin sheets that thickness is 0.3mm with the single screw extrusion machine that T mouth mould is installed.Total light transmittance, mist degree and plastic temperature range to resulting sheet are estimated, and with the results are shown in Table 14.
For the purpose of contrast, the forming composition (Comparative Examples 31 and 32) that does not add the extrusion moulding thing (Comparative Examples 30) that contains the teflon mixture powder and be added with fine polytetrafluoroethylpowder powder end (by the Fluon CD123 of Asahi ICI Fluoropolymers production) is estimated in an identical manner.The results are shown in Table 13.
Table 14
| Form (weight part) | Embodiment | Comparative Examples | ||
| 30 | 30 | 31 | 32 | |
| PP | 30 | 100 | 100 | 100 |
| Talcum | 100 | 30 | 30 | 30 |
| C-9 | 0.25 | |||
| CD123 | 0 | 0.1 | 1.0 | |
| Gloss (%) | 88 | 89 | 43 | 37 |
| Plastic temperature range (℃) | 20 | 2 | 3 | 3 |
Industrial applicibility
Melt tension reinforcing agent of the present invention has extraordinary dispersiveness in vistanex, the polyolefine resin composition that contains it has higher tension force when melting, and have good moulding processability, such as tensile property, hot formability, blow molding and the foaming etc. of calendering. The composition that contains melt tension reinforcing agent of the present invention can be used for preparing and has improved surface appearance and gratifying sheet material and the film extrusion moulding product of extruding processing characteristics. When being added with filler, roll and when extruding sheet material and film have improved surface appearance, also have simultaneously good hardness.
And, carry out the regeneration of vistanex waste material by adding melt tension reinforcing agent of the present invention, when melting, can prevent the reduction of tension force, and keep gratifying moulding processability, comprise tensile property, hot formability, blow molding and the foaming etc. of calendering. Its dispersiveness very high in vistanex also so that again raw product have gratifying appearance.
Therefore melt tension reinforcing agent of the present invention is highly suitable for producing the vistanex moulded products.
Claims (12)
1. polyolefin resin melt tension toughener, this toughener contain (A) tetrafluoroethylene and (B) alkyl acrylate of 5～30 carbon atoms or the polymkeric substance of alkyl methacrylate, and weight ratio (B)/(A) is 0.2-100.
2. a polyolefin resin for preparing claim 1 is with the method for melt tension toughener, this method comprises, mix the aqueous dispersion contain the tetrafluoroethylene that particle diameter is 0.05～1.0 μ m (A) particle and contain the alkyl acrylate of 5～30 carbon atoms that particle diameter is 0.05～1.0 μ m or the aqueous dispersion of polymkeric substance (B) particle of alkyl methacrylate, condense this mixture then or it is carried out spraying drying, obtain powder.
3. a polyolefin resin for preparing claim 1 is with the method for melt tension toughener, this method comprises, at the aqueous dispersion that contains the tetrafluoroethylene that particle diameter is 0.05～1.0 μ m (A) particle with contain in the dispersion of mixture of aqueous dispersion of polymkeric substance (B) particle of the alkyl acrylate of 5～30 carbon atoms that particle diameter is 0.05～1.0 μ m or alkyl methacrylate, polymerization contains the monomer that ethene belongs to unsaturated link(age), condense this product then or it is carried out spraying drying, obtain powder.
4. polyolefine resin composition, the polyolefin resin that it contains claim 1 is with melt tension toughener and (C) polyolefin resin.
5. polyolefine resin composition with good moulding processability, said composition is to obtain with the melt tension toughener by the polyolefin resin that adds claim 1 or 4 in polyolefin resin, wherein based on 100 weight part polyolefin resines, (A) content of tetrafluoroethylene is 0.001～20 weight part.
6. the circulation means of polyolefin resin goods, wherein for recycling, polyolefin resin goods waste material is cut or pulverizes and carries out the heat fusing moulding, this method comprises the polyolefin resin melt tension toughener that adds claim 1 or 4 in polyolefin resin goods waste material, wherein based on the polyolefin resin in the described polyolefin resin goods of the 100 weight parts waste material, (A) content of tetrafluoroethylene is 0.001～20 weight part.
7. method for preparing polyolefin resin foam, this method is included in the polyolefin resin of melt kneading claim 1 in the forcing machine or 4 with melt tension toughener, polyolefin resin and whipping agent, extrudes this mixture by a mouth mould that is installed in the forcing machine end under lower blow(ing) pressure then.
8. method for preparing polyolefin resin foam, this method is included in the polyolefine resin composition and the whipping agent of melt kneading claim 5 in the forcing machine, extrudes this mixture by a mouth mould that is installed in the forcing machine end under lower blow(ing) pressure then.
9. claim 7 or 8 method, wherein polyolefin resin is essentially no crosslinked acrylic resin.
10. claim 7 or 8 method, wherein polyolefin resin is an alfon.
11. the polyolefin sheets that obtains of polyolefine resin composition by calendering claim 5.
12. the polyolefin sheets that thermoforming is used, this sheet material contains the polyolefine resin composition of claim 5.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP226834/1997 | 1997-08-22 | ||
| JP22683297 | 1997-08-22 | ||
| JP22683497A JP3260307B2 (en) | 1997-08-22 | 1997-08-22 | How to Recycle Polyolefin Resin Products |
| JP226832/1997 | 1997-08-22 | ||
| JP00676998A JP3277148B2 (en) | 1998-01-16 | 1998-01-16 | Method for producing foamed foam of propylene resin |
| JP6769/1998 | 1998-01-16 | ||
| JP1112198A JP3209955B2 (en) | 1998-01-23 | 1998-01-23 | Polyolefin resin composition for calender molding |
| JP11121/1998 | 1998-01-23 | ||
| JP12846/1998 | 1998-01-26 | ||
| JP01284698A JP3280904B2 (en) | 1998-01-26 | 1998-01-26 | Polyolefin sheet for thermoforming |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1271372A CN1271372A (en) | 2000-10-25 |
| CN1168775C true CN1168775C (en) | 2004-09-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB98809360XA Expired - Lifetime CN1168775C (en) | 1997-08-22 | 1998-08-21 | Melt tension improver for polyolefen resins and process for producing the same |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6344493B2 (en) |
| KR (1) | KR100526961B1 (en) |
| CN (1) | CN1168775C (en) |
| WO (1) | WO1999010431A1 (en) |
Cited By (1)
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|---|---|---|---|---|
| CN105940333A (en) * | 2014-01-17 | 2016-09-14 | 三菱丽阳株式会社 | Optical fiber cable and sensor |
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| JP4936346B2 (en) | 1999-01-27 | 2012-05-23 | テトラ ラバル ホールディングス アンド ファイナンス エス エイ | Laminated packaging for paper containers |
| US6639020B1 (en) * | 1999-09-03 | 2003-10-28 | Exxon Mobil Chemical Patents Inc. | Plasticized polypropylene thermoplastics |
| JP2003523434A (en) * | 2000-02-16 | 2003-08-05 | アドバンスド エラストマー システムズ，エル．ピー． | Thermoplastic elastomers with improved foaming and physical properties |
| ATE328959T1 (en) * | 2001-03-01 | 2006-06-15 | Borealis Tech Oy | POLYETHYLENE MIXTURES FOR ROTARY CASTING |
| KR100879871B1 (en) * | 2001-05-08 | 2009-01-22 | 미쯔비시 레이온 가부시끼가이샤 | Modifier for thermoplastic resin and thermoplastic resin composition containing the same |
| WO2003022923A1 (en) * | 2001-09-11 | 2003-03-20 | Daikin Industries, Ltd. | Fluorine-containing resin composition, method for producing the same, and cable having coating comprising the same |
| KR100808723B1 (en) * | 2001-12-27 | 2008-02-29 | 삼성토탈 주식회사 | Composition for producing high melt strength polypropylene |
| US20040038018A1 (en) * | 2002-08-22 | 2004-02-26 | Trexel, Inc. | Thermoplastic elastomeric foam materials and methods of forming the same |
| GB0319467D0 (en) * | 2003-08-19 | 2003-09-17 | Bp Chem Int Ltd | Polymer blends |
| EP1767583B1 (en) * | 2004-06-25 | 2013-11-27 | Daikin Industries, Ltd. | Resin composition and moldings thereof |
| US7727606B2 (en) * | 2004-11-02 | 2010-06-01 | Jsp Corporation | Polylactic acid resin foamed molding and process for manufacturing the same |
| US20060135691A1 (en) * | 2004-11-22 | 2006-06-22 | Phillips Plastics Corporation | Foaming additives |
| US20060292357A1 (en) * | 2004-11-22 | 2006-12-28 | Phillips Plastics Corporation | Additives for foaming polymeric materials |
| KR101126016B1 (en) * | 2005-10-04 | 2012-03-19 | 주식회사 엘지화학 | Method for preparing graft rubber latex having low residual monomer content |
| US20070123655A1 (en) * | 2005-11-30 | 2007-05-31 | Gaggar Satish K | Weatherable, high modulus polymer compositions and method |
| JP5497410B2 (en) * | 2008-11-14 | 2014-05-21 | 三井化学株式会社 | Foam and production method thereof |
| TWI568784B (en) * | 2009-04-10 | 2017-02-01 | 三菱麗陽股份有限公司 | Additive for thermoplastic resin, production method thereof, thermoplastic resin composition and shaped article |
| KR101419618B1 (en) * | 2009-11-26 | 2014-07-14 | 미츠비시 레이온 가부시키가이샤 | Processing aid for polyolefin resins, polyolefin resin compositions, and molded products |
| WO2013031644A1 (en) * | 2011-08-26 | 2013-03-07 | 三菱レイヨン株式会社 | Polytetrafluoroethylene-containing powder, polycarbonate resin composition containing said powder, and molded product of said composition |
| CN105612201B (en) | 2013-10-10 | 2019-05-03 | 瑞西诺色彩株式会社 | Masterbatch, masterbatch group, the manufacturing method of masterbatch and forming synthetic resin product |
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1998
- 1998-08-21 US US09/463,996 patent/US6344493B2/en not_active Expired - Lifetime
- 1998-08-21 KR KR10-2000-7001717A patent/KR100526961B1/en not_active IP Right Cessation
- 1998-08-21 CN CNB98809360XA patent/CN1168775C/en not_active Expired - Lifetime
- 1998-08-21 WO PCT/JP1998/003718 patent/WO1999010431A1/en active IP Right Grant
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105940333A (en) * | 2014-01-17 | 2016-09-14 | 三菱丽阳株式会社 | Optical fiber cable and sensor |
| CN105940333B (en) * | 2014-01-17 | 2020-01-07 | 三菱化学株式会社 | Optical cable and sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1999010431A1 (en) | 1999-03-04 |
| US20010016627A1 (en) | 2001-08-23 |
| KR20010023095A (en) | 2001-03-26 |
| CN1271372A (en) | 2000-10-25 |
| KR100526961B1 (en) | 2005-11-08 |
| US6344493B2 (en) | 2002-02-05 |
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